Analytical and Bioanalytical Chemistry

, Volume 406, Issue 22, pp 5359–5367 | Cite as

Thermoresponsive ketoprofen-imprinted monolith prepared in ionic liquid

  • Xuan Sun
  • Chun-Yan Zhao
  • Xian-Hua Wang
  • Yan-Ping Huang
  • Zhao-Sheng LiuEmail author
Research Paper


A thermoresponsive imprinted monolith with the ability of molecular recognition for ketoprofen was prepared for the first time. The smart monolith was synthesized in a stainless steel column using acrylamide (AAm) and 2-acrylamide-2-methyl propanesulfonic acid (AMPS) as functional monomers, which can form interpolymer complexation to restrict access of the analyte to the imprinted networks at low temperatures. To avoid a high back pressure of the column derived from neat dimethyl sulfoxide (DMSO) as a porogenic solvent that is needed to solve polar AMPS, an ionic liquid, [BMIM]BF4, was introduced into the pre-polymerization mixture. The molecular recognition ability towards ketoprofen of the resulting thermoresponsive molecularly imprinted polymer (MIP) monolith displayed significant dependence on temperature compared with a non-imprinted column (NIP), and the greatest imprinting factor was achieved at the transition temperature of 35 °C (above 10). Furthermore, the number of binding sites of the smart MIP monolith at 35 °C was about 76 times as large as that at 25 °C. In addition, Freundlich analyses indicated that the thermoresponsive MIP monolith had homogeneous affinity sites at both 25 and 35 °C with heterogeneity index 0.9251 and 0.9851, respectively.


Molecularly imprinted polymer Ketoprofen Monolith Thermoresponsive Molecular recognition 



This work was supported by the National Natural Science Foundation of China (Grant No. 21375096).

Supplementary material

216_2014_7932_MOESM1_ESM.pdf (688 kb)
ESM 1 (PDF 687 kb)


  1. 1.
    Yan M (2004) Molecularly imprinted materials: science and technology. CRC PressGoogle Scholar
  2. 2.
    Sellergren B (2000) Molecularly imprinted polymers: man-made mimics of antibodies and their application in analytical chemistry. ElsevierGoogle Scholar
  3. 3.
    Liang RN, Song DA, Zhang RM, Qin W (2010) Angew Chem Int Ed 49:2556CrossRefGoogle Scholar
  4. 4.
    Zhao YJ, Zhao XW, Hu J, Li J, Xu WY, Gu ZZ (2009) Angew Chem Int Ed 48:7350CrossRefGoogle Scholar
  5. 5.
    Nematollahzadeh A, Sun W, Aureliano CSA, Lutkemeye D, Stute J, Abdekhodaie MJ, Shojaei A, Sellergren B (2011) Angew Chem Int Ed 50:495CrossRefGoogle Scholar
  6. 6.
    Lin Z, Yang F, He XW, Li WY, Zhao XM, Zhang YK (2009) J Chromatogr A 1216:8612CrossRefGoogle Scholar
  7. 7.
    Zheng C, Huang YP, Liu ZS (2013) Anal Bioanal Chem 405:2147CrossRefGoogle Scholar
  8. 8.
    Yan H, Sun N, Han Y, Yang C, Wang M, Wu R (2013) J Chromatogr A 1307:21CrossRefGoogle Scholar
  9. 9.
    Basozabal I, Gomez-Caballero A, Diaz-Diaz G, Guerreiro A, Gilby S, Goicolea MA, Barrio RJ (2013) J Chromatogr A 1308:45CrossRefGoogle Scholar
  10. 10.
    Resmini M (2012) Anal Bioanal Chem 402:3021CrossRefGoogle Scholar
  11. 11.
    Urraca JL, Moreno-Bondi MC, Orellana G, Sellergren B, Hall AJ (2007) Anal Chem 79:4915CrossRefGoogle Scholar
  12. 12.
    Liu JQ, Wullf G (2008) J Am Chem Soc 130:8044CrossRefGoogle Scholar
  13. 13.
    Muratsugu S, Tada M (2013) Acc Chem Res 46:300CrossRefGoogle Scholar
  14. 14.
    Tan J, Wang HF, Yan XP (2009) Anal Chem 81:5273CrossRefGoogle Scholar
  15. 15.
    González GP, Hernando PF, Alegría JSD (2008) Biosens Bioelectron 23:1754CrossRefGoogle Scholar
  16. 16.
    Henry OYF, Piletsky SA, Cullen DC (2008) Biosens Bioelectron 23:1769CrossRefGoogle Scholar
  17. 17.
    Suedee R, Seechamnanturalit V, Canyuk B, Ovatlarnporn C, Martin GP (2006) J Chromatogr A 1114:239CrossRefGoogle Scholar
  18. 18.
    Li S, Ge Y, Tiwari A, Wang S, Turner APF, Piletsky SA (2011) J Catal 278:173CrossRefGoogle Scholar
  19. 19.
    Li S, Ge Y, Turner APF (2011) Adv Funct Mater 21:1194CrossRefGoogle Scholar
  20. 20.
    Li S, Ge Y, Piletsky S, Turner APF (2011) Adv Funct Mater 21:3344CrossRefGoogle Scholar
  21. 21.
    Qin L, He XW, Yuan X, Li WY, Zhang YK (2011) Anal Bioanal Chem 399:3375CrossRefGoogle Scholar
  22. 22.
    Kanekiyo Y, Naganawa R, Tao H (2003) Angew Chem Int Ed 42:3014CrossRefGoogle Scholar
  23. 23.
    Fang L, Chen S, Zhang Y, Zhang H (2011) J Mater Chem 21:2320Google Scholar
  24. 24.
    McPhee W, Tam KC, Pelton R (1993) J Colloid Interface Sci 156:24CrossRefGoogle Scholar
  25. 25.
    Zrínyi M (2000) Colloid Polym Sci 278:98CrossRefGoogle Scholar
  26. 26.
    Miyata T, Jige M, Nakaminami T, Uragami T (2006) Proc Natl Acad Sci U S A 103:1190CrossRefGoogle Scholar
  27. 27.
    Ou J, Kong L, Pan C, Su X, Lei X, Zou H (2006) J Chromatogr A 1117:163CrossRefGoogle Scholar
  28. 28.
    Liu H, Zhuang X, Turson M, Zhang M, Dong X (2008) J Sep Sci 31:1694CrossRefGoogle Scholar
  29. 29.
    Li XX, Bai LH, Wang H, Wang J, Huang YP, Liu ZS (2012) J Chromatogr A 1251:141CrossRefGoogle Scholar
  30. 30.
    Li H, Liu YJ, Zhang ZH, Liao HP, Nie LH, Yao SZ (2005) J Chromatogr A 1098:66CrossRefGoogle Scholar
  31. 31.
    Sellergren B (1994) Anal Chem 66:1678CrossRefGoogle Scholar
  32. 32.
    Li ZY, Liu ZS, Zhang QW, Duan HQ (2007) Chin Chem Lett 18:322CrossRefGoogle Scholar
  33. 33.
    Zhao L, Ban L, Zhang QW, Huang YP, Liu ZS (2011) J Chromatogr A 1218:9071CrossRefGoogle Scholar
  34. 34.
    Yin JF, Yang GL, Chen Y (2005) J Chromatogr A 1090:68CrossRefGoogle Scholar
  35. 35.
    Booker K, Bowyer MC, Holdsworth CI, McCluskey A (2006) Chem Commun 11:1730CrossRefGoogle Scholar
  36. 36.
    Bai LH, Chen XX, Huang YP, Zhang QW, Liu ZS (2013) Anal Bioanal Chem 405:8935CrossRefGoogle Scholar
  37. 37.
    Lin JM, Nakagama T, Uchiyama K, Hobo T (1997) Biomed Chromatogr 11:298CrossRefGoogle Scholar
  38. 38.
    Sing KSW (1982) Pure Appl Chem 54:2201CrossRefGoogle Scholar
  39. 39.
    Spegel P, Schweiz L, Nilsson S (2001) Electrophoresis 22:3833CrossRefGoogle Scholar
  40. 40.
    Andersson HS, Karlsson JG, Piletsky SA, Koch-Schmidt AC, Mosbach K, Nicholls IA (1999) J Chromatogr A 848:39CrossRefGoogle Scholar
  41. 41.
    Urracaa JL, Carbajo MC, Torralvob MJ, González-Vázquezc J, Orellanad G, Moreno-Bondi MC (2008) Biosens Bioelectron 24:155CrossRefGoogle Scholar
  42. 42.
    Chen Y, Kele M, Quinones I, Sellergren B, Guiochon G (2001) J Chromatogr A 927:1CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Xuan Sun
    • 1
  • Chun-Yan Zhao
    • 1
  • Xian-Hua Wang
    • 1
  • Yan-Ping Huang
    • 1
  • Zhao-Sheng Liu
    • 1
    Email author
  1. 1.Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics (Theranostics), School of PharmacyTianjin Medical UniversityTianjinChina

Personalised recommendations